CN110964040A - Benzoxadiazole-based acceptor material and preparation method and application thereof - Google Patents
Benzoxadiazole-based acceptor material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic solar cells, and particularly relates to a benzoxazole-based acceptor material. The benzoxazole-based acceptor material provided by the invention has the advantages of wide ultraviolet visible light spectrum absorption bandwidth (350-2) Larger open circuit voltage (0.74V) and higher photoelectric conversionThe efficiency (4.41%) and the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of organic solar cells, and particularly relates to a benzoxadiazole-based acceptor material and a preparation method thereof, and application of the acceptor material in organic solar cells.
Background
With the increasing severity of energy problems, the development of novel energy is in need, and solar energy has great development prospect due to the advantages of cleanness, no pollution, inexhaustibility, and the like. How to better utilize solar energy is a key solution for dealing with energy crisis. Organic solar cells (OPVs) use organic conjugated molecules as active materials, have many advantages such as light weight, flexibility, wide raw material sources, low cost, solution processibility, large-area fabrication, etc., and have attracted extensive attention in the global academic and industrial fields. The photosensitive active layer material is a host material for converting sunlight into electric energy, is a key factor for determining the performance of the organic solar cell, and generally consists of a donor material and an acceptor material. The development and continuous development progress of conjugated molecular materials are the source of the improvement of the performance of organic solar cells, and in recent years, many kinds of organic conjugated compounds including conjugated macromolecules, conjugated small molecules, fullerene and the like are widely applied to the active layers of the cells, and remarkable results are obtained. In the development process of organic solar cells, polymer solar cells based on fullerene receptors have excellent performance in terms of receptor materials, and are widely researched and focused by scientists, and fullerene derivatives have been dominating as receptor materials for a long time. However, fullerene derivatives have problems of instability, high cost, weak absorption in a visible light region, difficult energy level regulation, poor polydispersity of molecular weight distribution, poor batch-to-batch repeatability and the like, so that scientists begin to search for photovoltaic materials capable of replacing the fullerene derivatives to adapt to practical production applications.
Organic conjugated molecules have excellent characteristics such as definite molecular structure and molecular weight, anisotropic conjugated skeleton, high purity, batch stability and the like, so that the research on solar cells is more and more popular. The performance of the organic photovoltaic material is determined by the chemical structure of the organic photovoltaic material, and in order to obtain a high-performance photovoltaic material, multiple aspects such as spectral absorption, electron energy level and carrier mobility need to be considered, which need to be adjusted through reasonable molecular design, so that the open-circuit voltage, short-circuit current, filling factor and photoelectric conversion efficiency of the device are improved. Therefore, it is still necessary to search for a new organic conjugated molecular acceptor material and improve the application of the organic photovoltaic material in the organic solar cell.
Disclosure of Invention
The embodiment of the invention aims to provide a benzoxazole-based acceptor material, and aims to provide a novel acceptor material with an organic conjugated structure, reduce the optical band gap of the organic solar cell acceptor material, improve the photoelectric conversion efficiency and improve the application of the organic conjugated acceptor material in a solar cell.
Another object of the embodiments of the present invention is to provide a method for preparing a benzoxazole-based acceptor material.
It is another object of an embodiment of the present invention to provide an organic solar cell.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the structural general formula of the receptor material based on the benzoxazole is shown as the following formula (I):
wherein A is selected from oxygen group elements, R11And R12Are each independently selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group of (a), a branch is formed adjacent to at least one carbon atom of the first three carbons attached to the N atom,
X1and X2Is an electron-withdrawing unit, said X1And X2Each independently selected from any one of the following electron withdrawing groups:
wherein R is2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements.
Correspondingly, the preparation method of the benzodioxole-based acceptor material comprises the following steps:
obtaining an aldehyde compound containing a benzoxydiazole unit and an electron-withdrawing compound;
obtaining a weakly alkaline catalyst, dissolving the catalyst, the aldehyde compound and the electron-withdrawing compound in an organic solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain a benzoxazole-based receptor material;
wherein the aldehyde compound containing the benzoxazole unit is as follows:
the electron-withdrawing compound is selected from any one of the following compounds:
wherein A is selected from oxygen group elements, R1Is selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group adjacent to at least one of the first three carbons attached to the N atom, R2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements.
An organic solar cell comprises a light-trapping active layer, wherein the light-trapping active layer contains the benzoxadiazole-based acceptor material or the benzoxadiazole-based acceptor material prepared by the method.
The benzoxazole-based acceptor material provided by the invention takes a unit containing benzoxazole as an electron-donating unit, and introduces strong electron-withdrawing groups rich in cyano groups at two ends of the electron-donating unit as electron-withdrawing units to form an organic micromolecule acceptor material with an A-D-A conjugated structure. Wherein, the electron-donating unit containing benzoxadiazole unit uses benzoxadiazole as intermediate acceptor unit, and two sides are connected with each otherAnd the thiophene donor unit forms a nitrogen-containing carbon bridge hepta-fused ring electron donor unit with a D-A-D structure, and the electron donor unit can effectively adjust energy level. According to the embodiment of the invention, based on the LUMO and HOMO energy levels of the benzodioxole acceptor material, the optical band gap of the acceptor material is reduced, and the carrier mobility is improved, so that the photoelectric conversion efficiency of the organic solar cell is improved. In addition, branched alkyl containing 16-30 carbon atoms is introduced to the side of the electron donor unit, so that the flatness of the central core fused ring unit can be improved, the charge mobility is improved, the space twist of an A-D-A organic conjugated molecular structure is increased, the molecular solubility is improved, and the intermolecular aggregation is reduced. The benzoxazole-based acceptor material provided by the invention has the advantages of wide ultraviolet visible light spectrum absorption bandwidth (350-1150nm), narrow optical band gap (1.08eV), strong light absorption capacity, good sunlight capturing capacity, good solubility, and easy dissolution in common organic solvents such as chloroform, chlorobenzene, toluene, xylene and the like, and can be applied to organic solar cell devices to enable the devices to have high short-circuit current (9.16 mA/cm)2) The high-efficiency photoelectric conversion device has large open-circuit voltage (0.74V) and high photoelectric conversion efficiency (4.41%), and has wide application prospect.
According to the preparation method of the benzoxazole-based receptor material, under the action of a weakly basic catalyst, an electron-withdrawing compound with active methylene is connected to two ends of an aldehyde compound containing a benzoxazole unit through a Knoevenagel condensation reaction to form an organic micromolecule receptor material with an A-D-A conjugated structure. The preparation method of the benzodioxole-based acceptor material provided by the invention has the advantages of mild conditions, simple and convenient operation, low preparation cost and high yield, and is beneficial to large-scale production and application.
The organic solar cell provided by the invention comprises the following active layers for light capture: the benzoxazole based acceptor material with ultraviolet visible light spectrum absorption bandwidth (350-The device has high short-circuit current (9.16 mA/cm)2) The high open-circuit voltage (0.74V) and the high photoelectric conversion efficiency reach 4.41 percent, and the application prospect is wide.
Drawings
FIG. 1 is a schematic diagram of the synthetic route for the benzothiadiazole-based acceptor material (IC-CN) provided in example 1 of the present invention.
FIG. 2 IS a schematic diagram of the synthetic route for the benzoselenadiazole-based acceptor material (IS-CN) provided in example 2 of the present invention.
FIG. 3 is an absorption spectrum of benzothiadiazole-based acceptor material (IC-CN) provided in example 1 of the present invention in chloroform solution and in a thin film state.
FIG. 4 is a cyclic voltammogram of a benzothiadiazole-based acceptor material (IC-CN) provided in example 1 of the present invention.
Fig. 5 is a current-voltage (J-V) graph of the organic solar cell provided in example 3 of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention,
etc. in the structures with a connecting bond, the connecting sites are indicated.
The embodiment of the invention provides an acceptor material based on benzoxadiazole, which has a structural general formula shown as the following formula (I):
wherein A is selected from oxygen group elements, R11And R12Are each independently selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group of (a), a branch is formed adjacent to at least one carbon atom of the first three carbons attached to the N atom,
X1and X2Is an electron-withdrawing unit, said X1And X2Each independently selected from any one of the following electron withdrawing groups:
wherein R is2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements.
According to the benzoxazole-based acceptor material provided by the embodiment of the invention, a unit containing benzoxazole is taken as an electron-donating unit, and strong electron-withdrawing groups rich in cyano groups are introduced at two ends of the electron-donating unit and taken as electron-withdrawing units, so that an organic micromolecule acceptor material with an A-D-A conjugated structure is formed. The electron donor unit with the benzoxydiazole unit is formed by taking benzoxydiazole as an intermediate acceptor unit and connecting thiophene donor units on two sides to form a nitrogen-containing carbon bridge hepta-condensed ring electron donor unit with a D-A-D structure, and the electron donor unit can effectively adjust LUMO and HOMO energy levels of the benzoxydiazole-based acceptor material, reduce the optical band gap of the acceptor material and improve the carrier mobility, so that the photoelectric conversion efficiency of the organic solar cell is improved. In addition, by introducing carbon-containing atoms at the side of the electron-donating unitsThe branched alkyl with the number of 16-30 can increase the flatness of the central core fused ring unit so as to improve the charge mobility, increase the space torsion of an A-D-A organic conjugated molecular structure, improve the molecular solubility and reduce the intermolecular aggregation. The benzoxazole-based acceptor material provided by the embodiment of the invention has the advantages of wide ultraviolet-visible light spectrum absorption bandwidth (350-1150nm), narrow optical band gap (1.08eV), strong light absorption capacity, good sunlight capturing capacity, good solubility, and easy dissolution in common organic solvents such as chloroform, chlorobenzene, toluene, xylene and the like, and can be applied to organic solar cell devices to enable the devices to have high short-circuit current (9.16 mA/cm)2) The high-efficiency photoelectric conversion device has large open-circuit voltage (0.74V) and high photoelectric conversion efficiency (4.41%), and has wide application prospect.
Specifically, in the benzoxazole-based acceptor material provided by the embodiment of the present invention, the electron-donating unit is a nitrogen-containing carbon-bridged hepta-fused ring structure containing a benzoxazole unit:
wherein A is selected from oxygen group elements, R11And R12Are each independently selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group, at least one carbon atom of the first three carbons adjacent to the N atom forms a branched chain, specifically a branched alkyl group having 16 to 30 carbon atoms, and in the branched alkyl group, at least one carbon atom of the first three carbons adjacent to the N atom forms a branched chain. The electron donor unit used in the embodiment of the invention takes benzoxadiazole as an intermediate acceptor unit, and two sides of the benzoxadiazole are connected with thiophene donor units to form a nitrogen-carbon bridge hepta-fused ring electron donor unit with a D-A-D structure, so that on one hand, the nitrogen-carbon bridge hepta-fused ring structure provides a highly flattened and rigidized long pi-conjugated system for electron transmission, the conjugated effect of the electron donor unit and the electron withdrawing unit is increased, and the charge transfer in organic acceptor molecules is facilitated; in another aspect, in hepta-fused ring donor unitsLone pair electrons of nitrogen atoms participate in conjugation, the electron cloud density of a conjugated system is increased, and the electron donating capability of the whole central core fused ring unit is further improved; the organic solar cell has the advantages that the organic solar cell is beneficial to the electron push-pull effect between the donor and acceptor units in the organic acceptor molecule, enhances the electron transmission in the molecule and between the molecules, can effectively adjust the LUMO and HOMO energy levels of the acceptor material, reduces the optical band gap of the acceptor material, and improves the carrier mobility, thereby improving the photoelectric conversion efficiency of the organic solar cell. In addition, C forming a branch chain is respectively introduced on the side chain adjacent to at least one carbon atom of the first three carbons connected on the N atom16～C30Branched alkyl radical R11And R12The material is placed on the outer side of a conjugate plane of the hepta-fused ring main body, so that the flatness of an electron supply unit of the hepta-fused ring can be increased, the charge mobility is further improved, the space twist of an A-D-A organic conjugate receptor molecule is increased, the molecular solubility can be effectively improved, and the intermolecular aggregation is reduced. In addition, R11And R12The organic conjugated molecule is independently selected from different branched alkyl groups, and the steric torsion of the organic conjugated molecule can be better improved by introducing different branched chains, so that the solubility is improved.
In the embodiment of the invention, benzothiadiazole or benzoselenadiazole is used as an intermediate acceptor unit of an electron donor unit, so that the light absorption band of the acceptor material is effectively widened, and the light absorption capacity of the acceptor material is improved.
As a preferred embodiment, said R11And said R12Each independently selected from:
in the embodiment of the invention, the number of carbon atoms for forming a branched chain on the second carbon atom close to the N atom is 16-3 introduced to the side edge of the hepta-condensed ring electron donor unitThe 0 branched alkyl group is more favorable for improving the flatness of the hepta-condensed ring electron donor unit so as to improve the charge mobility, increase the space twist of the A-D-A organic conjugated acceptor molecule, effectively improve the molecule solubility and reduce the aggregation among molecules, so that the acceptor material based on the benzoxazole provided by the embodiment of the invention has better solubility and is easy to dissolve in common organic solvents such as chloroform, chlorobenzene, toluene, xylene and the like.
In some embodiments, a in the nitrogen-containing carbon-bridged hepta-fused ring structure containing a benzoxazole unit is selected from sulfur or selenium; the R is11And said R12Each independently selected from:
specifically, the embodiment of the invention provides an electron-withdrawing unit X in the benzoxazole-based acceptor material1And X2Each independently selected from the following cyano-rich electron-withdrawing groups with strong electron-withdrawing ability:
wherein R is2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements. The electron-withdrawing unit used in the embodiment of the invention is rich in electron-withdrawing groups such as cyano-group, fluorine, chlorine, methoxy group, sulfoxy group and the like, so that the electron-withdrawing unit has strong electron-withdrawing capability, a push-pull system of electrons in acceptor molecules is enhanced, intramolecular charge transfer is facilitated, the LUMO energy level of the material can be effectively reduced, and the electron-withdrawing unit is better matched with the electron-donating unit in the embodiment of the invention. The electron-withdrawing group provided by the embodiment of the invention and the electron-donating unit containing the benzoxazine oxadiazole unit and having the nitrogen-carbon bridge hepta-condensed ring structure form an organic conjugated molecule with an A-D-A structure, and the organic conjugated molecule has the advantages of high intramolecular charge transfer degree, strong light absorption capacity, narrow optical band gap, and charge carrier mobilityHigh in electron mobility, and is an ideal material for an electron acceptor in an active layer of an organic solar cell.
In some embodiments, the electron-withdrawing unit in the benzoxazole-based acceptor material is the following cyano-rich group with strong electron-withdrawing ability:
wherein R is2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen, sulfur or selenium.
As a preferred embodiment, said R11And said R12Selected from the same said C16～C30A branched alkyl group of (2), said X1And said X2Selected from the same said electron withdrawing groups. The benzoxazole-based acceptor material in the embodiment of the invention is an organic conjugated molecule with a symmetrical structure, so that the synthesis efficiency is higher, and the preparation process is simpler.
In some embodiments, the receptor material has the formula:
in some embodiments, the receptor material has the formula:
in some embodiments, the receptor material has the formula:
the benzoxazole-based acceptor material provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention also provides a preparation method of the benzodioxole-based acceptor material, which comprises the following steps:
s10, obtaining an aldehyde compound and an electron-withdrawing compound containing a phenoxy oxadiazole unit;
s20, obtaining a weakly alkaline catalyst, dissolving the catalyst, the aldehyde compound and the electron-withdrawing compound in an organic solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain a benzodioxole-based receptor material;
wherein the aldehyde compound containing the benzoxazole unit is as follows:
the electron-withdrawing compound is selected from any one of the following compounds:
wherein A is selected from oxygen group elements, R1Is selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group adjacent to at least one of the first three carbons attached to the N atom, R2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements.
According to the preparation method of the benzoxazole-based receptor material provided by the embodiment of the invention, under the action of a weakly basic catalyst, an electron-withdrawing compound with active methylene is connected to two ends of an aldehyde compound containing a benzoxazole unit through a Knoevenagel condensation reaction to form an organic micromolecule receptor material with an A-D-A conjugated structure. The preparation method of the benzodioxole-based acceptor material provided by the embodiment of the invention has the advantages of mild conditions, simple and convenient operation, low preparation cost and high yield, and is beneficial to large-scale production and application. The benzodioxole-based acceptor material prepared by the embodiment of the invention has the advantages of spectral absorption bandwidth (350-1150nm), narrow optical band gap (1.08eV), strong light absorption capacity, good sunlight capturing capacity and photoelectric conversion efficiency, good solubility, easy dissolution in common organic solvents such as chloroform, chlorobenzene, toluene, xylene and the like, and wide application prospect.
Specifically, in the above step S10, the aldehyde-based compound containing a benzoxazole unit and the electron-withdrawing compound are obtained. Wherein the aldehyde compound containing the benzoxazole unit is as follows:
the electron-withdrawing compound is selected from any one of the following compounds:
wherein A is selected from oxygen group elements, R1Is selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group adjacent to at least one of the first three carbons attached to the N atom, R2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements. In the embodiment of the invention, an aldehyde compound containing a phenoxy oxadiazole unit and an electron-withdrawing compound rich in cyano are used as raw materials to synthesize an organic micromolecule acceptor material with an A-D-A conjugated structure, wherein the unit of the nitrogen-containing carbon bridge hepta-fused ring is used as an electron-donating unit, and the electron-withdrawing group rich in cyano is used as an electron-withdrawing unit, and the characteristics and advantages of the nitrogen-containing carbon bridge hepta-fused ring electron-donating unit and the electron-withdrawing unit rich in cyano are discussed previously and are not repeated herein.
In some embodiments, the a is selected from: sulfur or selenium. The T is selected from: oxygen, sulfur or selenium; the R is1Selected from:
specifically, in step S20, a weakly basic catalyst is obtained, and the catalyst, the aldehyde compound, and the electron-withdrawing compound are dissolved in an organic solvent, and then refluxed for 12-24 hours at 60-70 ℃ to obtain the benzodioxole-based acceptor material. According to the embodiment of the invention, the aldehyde compound and the electron-withdrawing compound are dissolved in an organic solvent through a weakly alkaline catalyst, the reflux is carried out for 12-24 hours at the temperature of 60-70 ℃, and the Knoevenagel condensation reaction is carried out on the aldehyde compound containing the benzoxazole unit and the electron-withdrawing compound containing the active methylene under the action of the catalyst, so that the receptor material based on the benzoxazole is obtained.
As a preferred example, the molar ratio of the aldehyde-based compound and the electron-withdrawing compound is 1: (4-20). The embodiment of the invention adopts the following components in a molar ratio of 1: (4-20) the aldehyde compound and the electron-withdrawing compound are in a reaction ratio, so that the Knoevenagel condensation reaction between the aldehyde compound containing the benzoxydiazole unit and the electron-withdrawing compound containing the active methylene is more complete, and the preparation efficiency and yield of the benzoxydiazole-based receptor material are further ensured.
As a preferred embodiment, the weakly basic catalyst is selected from: piperidine, pyridine or quinoline. The piperidine, pyridine or quinoline catalyst selected in the embodiment of the invention has high catalytic efficiency, and can effectively catalyze Knoevenagel condensation reaction between an aldehyde compound containing a benzodiazole unit and an electron-withdrawing compound containing active methylene, and an organic micromolecule receptor material with an A-D-A conjugated structure. More preferably, the weakly basic catalyst is selected from pyridine.
As a preferred embodiment, the organic solvent is selected from: chloroform or dichloromethane. The chloroform or dichloromethane organic solvent used in the embodiment of the invention has a good dissolving effect on aldehyde compounds containing phenoxy oxadiazole units and electron-withdrawing compounds containing active methylene, so that the raw material compounds are fully dissolved, full contact reaction among the raw material compounds in the condensation reaction process is facilitated, the reaction efficiency is improved, and the yield of the organic micromolecule acceptor material with an A-D-A conjugated structure is improved.
In some embodiments, the benzoxazole-based acceptor material is prepared by: and (2) obtaining a weakly alkaline catalyst, dissolving the pyridine catalyst, the aldehyde compound and the electron-withdrawing compound in a chloroform solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain the benzodioxole-based receptor material.
As a preferred embodiment, the synthesis of the aldehyde-based compound containing a benzoxadiazole unit comprises the following steps:
s11, obtaining a bithiophene pyrrole compound, and carrying out unilateral bromination treatment on the bithiophene pyrrole compound under the action of N-bromosuccinimide to obtain a compound B;
s12, carrying out base catalysis bromine transfer treatment on the compound B under the action of lithium diisopropylamide to obtain a compound C;
s13, carrying out lithiation treatment on the compound C under the action of n-butyllithium to obtain a compound D;
s14, carrying out oxidation closed-loop treatment on the compound D under the action of ferric trichloride to obtain a compound E;
s15, oximation treatment is carried out on the compound E under the action of hydroxylamine hydrochloride to obtain a dioxime compound F;
s16, carrying out reduction treatment on the compound F under the action of hydrazine hydrate and a palladium-carbon catalyst to obtain a compound G;
s17, carrying out closed-loop treatment on the compound G under the action of thionyl chloride or selenium dioxide to obtain a compound H;
s18, formylating the compound H under the action of phosphorus oxychloride and N, N-dimethylformamide to obtain an aldehyde compound containing the benzodioxole unit;
wherein, the structural general formula of the bithiophene pyrrole compound is as follows:
the R is1Is selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group of (a), a branch is formed adjacent to at least one carbon atom of the first three carbons attached to the N atom.
The preparation method of the aldehyde compound containing the phenoxy diazole unit takes the benzodithiophene pyrrole compound as a raw material, and synthesizes the aldehyde compound containing the phenoxy diazole unit through a series of processing steps of unilateral bromination processing, bromine migration processing, lithiation processing, oxidative ring closure processing, oximation processing, reduction processing, formylation processing and the like. The aldehyde compound containing the benzoxazole unit can be obtained by the preparation method, and the preparation method is simple in operation, clear in synthetic route and high in synthetic efficiency.
Specifically, in step S11, a bithiophene pyrrole compound is obtained, and the bithiophene pyrrole compound is subjected to unilateral bromination under the action of N-bromosuccinimide (NBS), so as to obtain a compound B. As a preferred embodiment, a bithiophene pyrrole compound is obtained, and the molar ratio of the bithiophene pyrrole compound to the N-bromosuccinimide is 1: (1-1.4) dissolving the compound in a tetrahydrofuran solvent, and stirring and reacting for 5-24 hours at room temperature to obtain the compound B. In the embodiment of the invention, a bithiophene pyrrole compound is used as a raw material, and bromination treatment is carried out under the action of N-bromosuccinimide (NBS), so as to obtain a brominated compound B, wherein the specific synthetic route is as follows:
specifically, in step S12, compound B is subjected to base-catalyzed bromine transfer treatment under the action of Lithium Diisopropylamide (LDA), so as to obtain compound C. As a preferred embodiment, the step of base-catalyzed bromine transfer treatment comprises: and dissolving the compound B and the lithium diisopropylamide in a tetrahydrofuran solvent, and reacting for 1-2 hours at the temperature of-70 to-85 ℃ to obtain a compound C. As a more preferred embodiment, the molar amount of said compound B and said lithium diisopropylamide is 1: (1-1.3). In the embodiment of the invention, the bromine element on the compound B can be transferred to the meta position of the sulfur element by carrying out base catalysis bromine transfer treatment on the compound B under the action of lithium diisopropylamide, and the specific synthetic route is as follows:
specifically, in step S13, the compound C is lithiated by the action of n-butyllithium to obtain a compound D. As a preferred embodiment, the step of lithiation treatment includes: dissolving the compound C in anhydrous tetrahydrofuran, adding the n-butyllithium at-50 to-78 ℃, and reacting for 60 to 150 minutes to obtain a first solution; adding copper bromide and lithium bromide into anhydrous tetrahydrofuran, stirring for 10-60 min, and cooling to-40 ℃ to obtain a second solution; dissolving oxalyl chloride in anhydrous tetrahydrofuran to obtain a third solution; and adding the first solution into the second solution, reacting for about 5-10 min, adding the third solution, reacting for 1-4 hours, and heating to room temperature to obtain the compound D. As a more preferred embodiment, the molar ratio of said compound C, said n-butyllithium, said copper bromide, said lithium bromide and said oxalyl chloride is 1: (1-1.1): (1-1.1): (0.4-0.5). In the embodiment of the invention, the compound C is lithiated with reagents such as n-butyllithium, copper bromide, lithium bromide, oxalyl chloride and the like, and a cross-coupling reaction is carried out to obtain a compound D, wherein the specific synthetic route is as follows:
specifically, in step S14, the compound D is subjected to oxidative ring closure treatment under the action of ferric trichloride to obtain a compound E. As a preferred embodiment, the step of oxidative ring closure treatment includes: and (3) taking dichloromethane as a solvent, adding anhydrous ferric trichloride, stirring for 30-120 seconds, adding the compound D, and reacting at room temperature for 1-4 hours to obtain the compound E. As a more preferred embodiment, the molar ratio of said compound D and said anhydrous ferric chloride is 1: (3-6). The compound D of the embodiment of the invention is subjected to oxidation ring-closing treatment under the action of ferric trichloride to obtain a compound E after ring closing, and the specific synthetic route is as follows:
specifically, in step S15, the compound E is oximated by hydroxylamine hydrochloride to obtain a dioxime compound F. As a preferred embodiment, the step of oximation treatment comprises: and under the protection of nitrogen, adding the compound E and the hydroxylamine hydrochloride into an absolute ethyl alcohol solvent, and heating and refluxing for about 10-40 hours to obtain the compound F. As a more preferred example, the ratio of the molar amounts of the compound E and the hydroxylamine hydrochloride is 1: (2.4-4). In the embodiment of the invention, the compound E and hydroxylamine hydrochloride are heated and refluxed in an ethanol solvent according to a proper proportion for oximation treatment, so that an oximated dioxime compound F can be obtained, and the specific synthetic route is as follows:
specifically, in step S16, the compound F is subjected to a reduction treatment under the action of hydrazine hydrate and a palladium-carbon catalyst to obtain a compound G. As a preferred embodiment, the step of reduction treatment includes: adding the compound F into an absolute ethyl alcohol solvent under protective gas, then adding the palladium-carbon, heating to 60-80 ℃, adding a hydrazine hydrate solution dissolved in absolute ethyl alcohol, and reacting for 24-72 hours at 80-90 ℃ to obtain the compound G. As a more preferred embodiment, the volume ratio of the dichloromethane, the thionyl chloride and the triethylamine is (15-60): 10: (2-1), wherein the mass ratio of the compound G to the dichloromethane is 1: (15-45). In the embodiment of the invention, the compound F is subjected to reduction treatment with hydrazine hydrate, palladium carbon catalyst and the like under the protection gas of nitrogen, argon, helium and the like to obtain a compound G, and the specific synthetic route is as follows:
specifically, in step S17, the compound G is subjected to reduction treatment under the action of thionyl chloride or selenium dioxide to obtain a compound H. The compound G of the embodiment of the invention can be reduced to obtain the hepta-condensed ring central nucleus compound H of benzothiadiazole or benzoselenadiazole.
In some embodiments, the step of closed loop processing comprises: under the protection of nitrogen, dissolving the compound G in dichloromethane, adding thionyl chloride and triethylamine at room temperature, and heating and refluxing for 2-10 hours to obtain the post-chemical substance H1. As a more preferred embodiment, the volume ratio of the dichloromethane, the thionyl chloride and the triethylamine is (15-60): 10: (2-1), wherein the mass ratio of the compound G to the dichloromethane is 1: (15-45), the specific synthetic route is as follows:
in some embodiments, the compound G is dissolved in absolute ethyl alcohol, the mixture is heated and refluxed, then the selenium dioxide aqueous solution is added, and the mixture is stirred and refluxed for 3-6 hours to obtain the compound H2. As a more optional example, the molar ratio of the compound G to the selenium dioxide is 1 (1-2), and the specific synthetic route is as follows:
specifically, in step S18, the compound H is formylated under the action of phosphorus oxychloride and N, N-dimethylformamide to obtain the aldehyde compound containing a benzoxydiazole unit. As a preferred implementation, the formylation treatment step comprises: and dissolving the compound H and the phosphorus oxychloride in N, N-dimethylformamide, and heating to 80-90 ℃ to react for 6-24 hours to obtain the aldehyde compound containing the benzoxydiazole unit. As a more preferable embodiment, the molar ratio of the compound H to the phosphorus oxychloride is 1 (10-30). In the embodiment of the invention, the compound H is formylated under the action of phosphorus oxychloride and N, N-dimethylformamide to obtain an aldehyde compound containing a benzodiazole unit, wherein a synthetic route of the aldehyde compound (I) containing the benzothiadiazole unit and a synthetic route of the aldehyde compound (J) containing the benzoselenadiazole unit are respectively as follows:
the embodiment of the invention also provides an organic solar cell, which comprises a light-trapping active layer, wherein the light-trapping active layer contains the benzoxadiazole-based acceptor material or the benzoxadiazole-based acceptor material prepared by the method.
According to the organic solar cell provided by the embodiment of the invention, the active layer for light capture comprises: the benzoxazole-based acceptor material with ultraviolet visible light spectrum absorption bandwidth (350-2) The high open-circuit voltage (0.74V) and the high photoelectric conversion efficiency reach 4.41 percent, and the application prospect is wide.
As a preferred embodiment, the benzoxazole-based acceptor material and the electron donor are made into an active layer for an organic solar cell device. The preparation method comprises the steps of mixing an acceptor material based on benzoxadiazole and an electron donor material, adding a proper solvent chloroform or chlorobenzene, heating and stirring to completely dissolve the materials, spin-coating the materials on conductive glass to prepare a layer of thin film, and preparing an electrode on the thin film to prepare a battery device.
As a preferred embodiment, the electron donor material is at least one selected from the group consisting of PBDB-T, PTB7-th, J61, J71, PBDB-T-2F and PBDB-T-2Cl, having the following structural formula:
as a preferred implementation, the molar ratio of said benzoxadiazole based acceptor material to said electron donor material is 1: (1-2).
In order to make the details of the above-described implementation and operation of the present invention clearly understandable to those skilled in the art and to make the examples of the present invention significantly manifest the advanced performance of the benzoxazole-based acceptor material and the preparation method and application thereof, the above-described technical solutions are illustrated below by a plurality of examples.
Example 1
A method for preparing a benzothiadiazole-based receptor material, which is shown in the synthetic route of the attached figure 1:
s10. in the following
An aldehyde compound containing a benzothiadiazole unit is synthesized as a raw material compound 1.
① dissolving compound 1(5.0g, 12.4mmol) in 100mL tetrahydrofuran, stirring at normal temperature, adding N-bromosuccinimide (2.21g, 12.4mmol) in portions, stirring at normal temperature for reaction for 12 hours, then adding 40mL saturated sodium sulfite solution, extracting with dichloromethane three times, then drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether, vacuum concentrating to obtain light yellow liquid, compound 2, yield 90.4%, MS (EI, m/z) 481.2;
② dissolving compound 2(4.0g, 8.3mmol) in 60mL tetrahydrofuran, cooling to-78 deg.C, stirring, gradually adding 4.35mL (8.7mmol) of 2M lithium diisopropylamide solution dropwise, reacting at 78 deg.C for 1 hr, adding water, quenching, extracting with diethyl ether, drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether, and vacuum concentrating to obtain light yellow liquid, compound 3, with yield of 85.6% MS (EI, M/z) 481.2;
③ dissolving compound 3(2.5g, 5.2mmol) in 30mL of anhydrous tetrahydrofuran, cooling to-78 deg.C, stirring, adding 2.5M n-butyllithium (2.1mL, 5.2mmol) gradually to the solution, then reacting at-78 deg.C for two hours to obtain a first solution, simultaneously, adding cuprous bromide (0.75g, 5.2mmol) and lithium bromide (0.45g, 5.2mmol) to 40mL of anhydrous tetrahydrofuran, then stirring to completely dissolve the solids, cooling to-40 deg.C to obtain a second solution, dissolving oxalyl chloride (0.33g, 2.6mmol) in 10mL of anhydrous tetrahydrofuran, then cooling to-40 deg.C to obtain a third solution, adding the first solution gradually to the second solution, stirring for 10min, then slowly adding the third solution to solution B, then reacting at-78 deg.C for two hours, then heating to room temperature, quenching with saturated ammonium chloride solution, then spin drying the tetrahydrofuran, extracting with silica gel column, drying to obtain a colorless yield of EI, eluting with silica gel, drying with silica gel column, eluting with 84M, and purifying with silica gel to obtain a colorless liquid, EI/z;
④ Anhydrous ferric chloride (1.27g, 7.8mmol) is added to 70mL of dichloromethane, nitrogen is introduced for protection, then stirring is carried out for 10min, then compound 4(2.2g, 2.6mmol) is added to the reaction solution, then stirring is carried out for two hours at room temperature, then quenching is carried out with 15mL of ice water, extraction is carried out with ethyl acetate, then drying is carried out with anhydrous sodium sulfate, purification is carried out by silica gel column, petroleum ether and dichloromethane are used as eluent, light yellow solid is obtained after vacuum concentration, namely compound 5 is obtained, the yield is 81.6%, MS (ESI, M/z) [ M + H]+859.4；
⑤ Compound 5(1.3g, 1.51mmol), hydroxylamine hydrochloride (0.26g, 3.8mmol) and absolute ethanol (100mL) were added to a 250mL flask under nitrogen, then heated under reflux for 20 hours, then a certain amount of water was added, extracted with ethyl acetate, then dried over anhydrous sodium sulfate, purified with silica gel column, eluting with petroleum ether, and concentrated under vacuum to give a pale yellow solid, Compound 6, in 71.5% yield MS (ESI, M/z) [ M + H ] M]+889.5；
⑥ Compound 6(1.1g, 1.24mmol) is added to 100mL of absolute ethanol, 10% palladium on carbon catalyst (1.8g) is added under nitrogen protection, then the solution is heated to 65 ℃, hydrazine hydrate (2mL) dissolved in absolute ethanol (3mL) is slowly dripped into the reaction solution, then the reaction is carried out for 40 hours, ethyl acetate is used for extraction, then anhydrous sodium sulfate is used for drying, silica gel column purification is carried out, petroleum ether and ethyl acetate are used as eluent, and light yellow solid, namely compound 7, is obtained after vacuum concentration, and the yield is 68.6％。MS(ESI，m/z)[M+H]+859.5；
⑦ Compound 7(0.8g, 0.93mmol) was dissolved in 30mL dichloromethane, thionyl chloride (6mL) and triethylamine (2mL) were slowly added to the solution under nitrogen at room temperature, then heated under reflux for 5 hours, cooled to room temperature, the reaction solution was slowly added to ice water, then extracted with ethyl acetate, dried over anhydrous sodium sulfate, purified with silica gel column, eluting with petroleum ether and dichloromethane, and concentrated under vacuum to give white solid, Compound 8, yield 86.7%. MS (ESI, M/z) [ M + H ] (M + H)]+875.4；
⑧ dissolving compound 8(0.5g, 0.56mmol) in 15mL of N, N-dimethylformamide, cooling the reaction system to 0 ℃ under the protection of nitrogen, slowly adding phosphorus oxychloride (5mL), reacting at 0 ℃ for 2 hours, heating to 90 ℃ for 12 hours, extracting with ethyl acetate, drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether and dichloromethane, and vacuum concentrating to obtain white solid, i.e. aldehyde compound containing benzothiadiazole unit, with a yield of 72.4%. MS (ESI, M/z) [ M + H ] compound]+943.4；
S20. in the following
For the electron-withdrawing compound, aldehyde compound (0.35g, 0.37mmol) containing benzothiadiazole unit, 1, 1-dicyanomethylene-3-indanone
(0.57g, 2.96mmol), pyridine (2mL) was dissolved in chloroform (25mL), refluxed overnight under nitrogen, and cooled to room temperature. Then, the mixture was extracted with chloroform and dried over anhydrous sodium sulfate. Purification on a silica gel column with dichloromethane as eluent gave after vacuum concentration a blue solid (IC-CN), the benzothiadiazole-based acceptor material, in 58.5% yield. MS (TOF, M/z) [ M + H [)]+1269.5；1HNMR(400MHz，CDCl3)δ8.15(s，2H)，7.36(dt，J＝7.6，3.6Hz，4H)，7.22(dt，J＝7.6，3.4Hz，4H)，3.65(d，J＝7.2Hz，4H)，1.31(t，J＝6.4Hz，2H)，1.25-1.08(m，24H)，0.92-0.84(m，12H)。
The absorption spectrograms of the benzothiadiazole-based receptor material prepared in the embodiment of the invention in solution and thin films are shown in figure 3, and as can be seen from figure 3, the benzothiadiazole-based receptor material prepared in the embodiment of the invention has very good ultraviolet light absorption (350-1150nm), a narrow optical band gap (1.08eV), which is 0.2-0.3 eV less than the optical band gap of a common non-fullerene receptor small molecule, and is beneficial to improving the photoelectric conversion efficiency.
The cyclic voltammogram of the benzothiadiazole-based acceptor material prepared in the embodiment of the invention is shown in fig. 4, and as can be seen from fig. 4, the HOMO level of the benzothiadiazole-based acceptor material prepared in the embodiment of the invention is-5.45 eV, the LUMO level is-3.95 eV, the energy gap is small and is-1.5 eV, and the electron transfer is facilitated.
Example 2
A method for preparing a benzoselenadiazole-based receptor material, which is shown in a synthetic route shown in the accompanying figure 2:
s10. in the following
An aldehyde group compound containing a benzoselenadiazole unit is synthesized as a raw material compound 1.
① dissolving compound 1(5.0g, 12.4mmol) in 100mL tetrahydrofuran, stirring at normal temperature, adding N-bromosuccinimide (2.21g, 12.4mmol) in portions, stirring at normal temperature for reaction for 12 hours, then adding 40mL saturated sodium sulfite solution, extracting with dichloromethane three times, then drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether, vacuum concentrating to obtain light yellow liquid, compound 2, yield 90.4%, MS (EI, m/z) 481.2;
② dissolving compound 2(4.0g, 8.3mmol) in 60mL tetrahydrofuran, cooling to-78 deg.C, stirring, gradually adding 4.35mL (8.7mmol) of 2M lithium diisopropylamide solution dropwise, reacting at 78 deg.C for 1 hr, adding water, quenching, extracting with diethyl ether, drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether, and vacuum concentrating to obtain light yellow liquid, compound 3, with yield of 85.6% MS (EI, M/z) 481.2;
③ dissolving compound 3(2.5g, 5.2mmol) in 30mL of anhydrous tetrahydrofuran, cooling to-78 deg.C, stirring, adding 2.5M n-butyllithium (2.1mL, 5.2mmol) gradually to the solution, then reacting at-78 deg.C for two hours to obtain a first solution, simultaneously, adding cuprous bromide (0.75g, 5.2mmol) and lithium bromide (0.45g, 5.2mmol) to 40mL of anhydrous tetrahydrofuran, then stirring to completely dissolve the solids, cooling to-40 deg.C to obtain a second solution, dissolving oxalyl chloride (0.33g, 2.6mmol) in 10mL of anhydrous tetrahydrofuran, then cooling to-40 deg.C to obtain a third solution, adding the first solution gradually to the second solution, stirring for 10min, then slowly adding the third solution to solution B, then reacting at-78 deg.C for two hours, then heating to room temperature, quenching with saturated ammonium chloride solution, then spin drying the tetrahydrofuran, extracting with silica gel column, drying to obtain a colorless yield of EI, eluting with silica gel, drying with silica gel column, eluting with 84M, and purifying with silica gel to obtain a colorless liquid, EI/z;
④ Anhydrous ferric chloride (1.27g, 7.8mmol) is added to 70mL of dichloromethane, nitrogen is introduced for protection, then stirring is carried out for 10min, then compound 4(2.2g, 2.6mmol) is added to the reaction solution, then stirring is carried out for two hours at room temperature, then quenching is carried out with 15mL of ice water, extraction is carried out with ethyl acetate, then drying is carried out with anhydrous sodium sulfate, purification is carried out by silica gel column, petroleum ether and dichloromethane are used as eluent, light yellow solid is obtained after vacuum concentration, namely compound 5 is obtained, the yield is 81.6%, MS (ESI, M/z) [ M + H]+859.4；
⑤ Compound 5(1.3g, 1.51mmol), hydroxylamine hydrochloride (0.26g, 3.8mmol) and absolute ethanol (100mL) were added to a 250mL flask under nitrogen, then heated under reflux for 20 hours, then a certain amount of water was added, extracted with ethyl acetate, then dried over anhydrous sodium sulfate, purified with silica gel column, eluting with petroleum ether, and concentrated under vacuum to give a pale yellow solid, Compound 6, in 71.5% yield MS (ESI, M/z) [ M + H ] M]+889.5；
⑥ Compound 6(1.1g, 1.24mmol) was added to 100mL absolute ethanol under nitrogenAfter 10% palladium on carbon catalyst (1.8g) was added, the solution was heated to 65 ℃ and hydrazine hydrate (2mL) dissolved in absolute ethanol (3mL) was slowly added dropwise to the reaction solution, followed by reaction for 40 hours. Extracted with ethyl acetate, and then dried over anhydrous sodium sulfate. Purifying with silica gel column, eluting with petroleum ether and ethyl acetate, and vacuum concentrating to obtain light yellow solid, compound 7, with yield of 68.6%. MS (ESI, M/z) [ M + H ]]+859.5；
⑦ dissolving compound 7(0.8g, 0.93mmol) in 50mL of a mixture of absolute ethanol and tetrahydrofuran, heating under reflux under nitrogen, gradually adding selenium dioxide (0.21g, 1.86mmol) dissolved in hot water (10mL) to the reaction solution, heating under reflux for 5 hours to complete the reaction, slowly adding the reaction solution to ice water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether and dichloromethane, and vacuum concentrating to obtain light yellow solid, compound 10, with yield of 79.5% MS (ESI, M/z) [ M + H/z ], [ M + H/z ]]+935.4；
⑧ dissolving compound 10(0.5g, 0.56mmol) in 15mL of N, N-dimethylformamide, cooling the reaction system to 0 ℃ under the protection of nitrogen, slowly adding phosphorus oxychloride (5mL), reacting at 0 ℃ for 2 hours, heating to 90 ℃ for 12 hours, extracting with ethyl acetate, drying with anhydrous sodium sulfate, purifying with silica gel column, eluting with petroleum ether and dichloromethane, and vacuum concentrating to obtain yellow solid, i.e. aldehyde compound containing benzoselenadiazole unit, with yield of 76.8%. MS (ESI, M/z) [ M + H ] compound]+991.4。
S20. in the following
For the electron-withdrawing compound, aldehyde compound (0.35g, 0.37mmol) containing benzoselenadiazole unit, 1, 1-dicyanomethylene-3-indanone
(0.57g, 2.96mmol), pyridine (2mL) was dissolved in chloroform (25mL), refluxed overnight under nitrogen, and cooled to room temperature. Then the mixture is extracted by chloroform and then,dried over anhydrous sodium sulfate. Purification on a silica gel column with dichloromethane as eluent gave after vacuum concentration a blue solid (IS-CN), the benzoselenadiazole based acceptor material, in 48.2% yield. MS (TOF, M/z) [ M + H [)]+1343.4；1HNMR(400MHz，CDCl3)δ8.17(s，2H)，7.38(dt，J＝7.6，3.6Hz，4H)，7.24(dt，J＝7.6，3.4Hz，4H)，3.66(d，J＝7.2Hz，4H)，1.32(t，J＝6.4Hz，2H)，1.26-1.09(m，24H)，0.94-0.83(m，12H)。
Example 3
A method for preparing an organic solar cell device and photovoltaic performance thereof.
Preparing a device: taking the benzothiadiazole-based acceptor material prepared in example 1 of the present invention as an acceptor material, taking a commercial PTB7-th as a donor material, and mixing the donor material and the acceptor material according to the ratio of 1: 1, weighing the mixture, using o-dichlorobenzene as a solvent and 1, 8-diiodooctane as an additive, uniformly stirring the mixture, performing spin coating, and then classifying the chips and selecting different temperatures for annealing treatment. And after the treatment is finished, the scraping cathode is used as an anode contact of the device. Then, the negative electrode was evaporated with aluminum.
Photovoltaic performance: according to the structure of the device: ITO/PEDOT PSS/PTB 7-th: an organic solar cell is manufactured by IC-CN/PDINO/Al, and a device is subjected to performance test, wherein a J-V curve chart of a serial number 2 is shown as an attached figure 5, and a specific test result is shown as the following table 1:
as can be seen from the test results, a higher short-circuit current (9.16 mA/cm) can be realized in the organic solar cell2) And the energy conversion efficiency (PCE is 4.41 percent), and has wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The acceptor material based on the benzoxazole is characterized in that the structural general formula of the acceptor material is shown as the following formula (I):
wherein A is selected from oxygen group elements, R11And R12Are each independently selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group of (a), a branch is formed adjacent to at least one carbon atom of the first three carbons attached to the N atom,
X1and X2Is an electron-withdrawing unit, said X1And X2Each independently selected from any one of the following electron withdrawing groups:
wherein R is2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements.
2. The benzoxazole-based acceptor material according to claim 1, wherein said a is selected from sulfur or selenium; and/or the presence of a gas in the gas,
the R is11And said R12Each independently selected from:
and/or the presence of a gas in the gas,
the T is selected from: oxygen, sulfur or selenium.
3. The benzoxazole-based acceptor material according to claim 2, wherein said R is11And said R12Selected from the same groupC16～C30A branched alkyl group of (2), said X1And said X2Selected from the same said electron withdrawing groups.
4. A preparation method of a benzoxadiazole-based acceptor material is characterized by comprising the following steps:
obtaining an aldehyde compound containing a benzoxydiazole unit and an electron-withdrawing compound;
obtaining a weakly alkaline catalyst, dissolving the catalyst, the aldehyde compound and the electron-withdrawing compound in an organic solvent, and refluxing for 12-24 hours at the temperature of 60-70 ℃ to obtain a benzoxazole-based receptor material;
wherein the aldehyde compound containing the benzoxazole unit is as follows:
the electron-withdrawing compound is selected from any one of the following compounds:
wherein A is selected from oxygen group elements, R1Is selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group adjacent to at least one of the first three carbons attached to the N atom, R2Selected from: hydrogen, fluorine, chlorine, cyano, methoxy, sulfoxy or methyl, and T is selected from oxygen group elements.
5. The method for preparing benzoxazole-based acceptor material according to claim 4, wherein the molar ratio of said aldehyde-based compound to said electron-withdrawing compound is 1: (4-20); and/or the presence of a gas in the gas,
the weakly basic catalyst is selected from: piperidine, pyridine or quinoline.
6. The process for the preparation of benzoxadiazole based acceptor material according to claim 5, wherein said organic solvent is selected from: chloroform or dichloromethane; and/or the presence of a gas in the gas,
the A is selected from: sulfur or selenium; and/or the presence of a gas in the gas,
the T is selected from: oxygen, sulfur or selenium; and/or the presence of a gas in the gas,
the R is1Selected from:
7. the method for preparing benzoxazole-based acceptor material according to any one of claims 4 to 6, wherein the synthesis of said benzoxazole-unit-containing aldehyde-based compound comprises the steps of:
obtaining a bithiophene pyrrole compound, and carrying out unilateral bromination treatment on the bithiophene pyrrole compound under the action of N-bromosuccinimide to obtain a compound B;
carrying out base catalysis bromine migration treatment on the compound B under the action of lithium diisopropylamide to obtain a compound C;
carrying out lithiation treatment on the compound C under the action of n-butyl lithium to obtain a compound D;
carrying out oxidation closed-loop treatment on the compound D under the action of ferric trichloride to obtain a compound E;
oximation treatment is carried out on the compound E under the action of hydroxylamine hydrochloride to obtain a dioxime compound F;
reducing the compound F under the action of hydrazine hydrate and palladium carbon catalyst to obtain a compound G;
carrying out closed-loop treatment on the compound G under the action of thionyl chloride or selenium dioxide to obtain a compound H;
performing formylation treatment on the compound H under the action of phosphorus oxychloride and N, N-dimethylformamide to obtain an aldehyde compound containing a benzodiazole unit;
wherein the content of the first and second substances,the structural general formula of the bithiophene pyrrole compound is as follows:
the structural formulas of the compound B, the compound C, the compound D, the compound E, the compound F, the compound G and the compound H are respectively as follows:
wherein A is selected from sulfur or selenium element, R1Is selected from C16～C30And said C is a branched alkyl group of16～C30In the branched alkyl group of (a), a branch is formed adjacent to at least one carbon atom of the first three carbons attached to the N atom.
8. The method of preparing a benzoxazole-based acceptor material according to claim 7, wherein said unilateral bromination step comprises: dissolving the bithiophene pyrrole compound and the N-bromosuccinimide in a tetrahydrofuran solvent, and stirring and reacting for 5-24 hours at room temperature to obtain a compound B; and/or the presence of a gas in the gas,
the step of base-catalyzed bromine transfer treatment comprises: dissolving the compound B and the lithium diisopropylamide in a tetrahydrofuran solvent, and reacting at-70 to-85 ℃ for 1 to 2 hours to obtain a compound C; and/or the presence of a gas in the gas,
the step of lithiation treatment includes: dissolving the compound C in anhydrous tetrahydrofuran, adding the n-butyllithium at-50 to-78 ℃, and reacting for 60 to 150 minutes to obtain a first solution; adding copper bromide and lithium bromide into anhydrous tetrahydrofuran, stirring for 10-60 min, and cooling to-40 ℃ to obtain a second solution; dissolving oxalyl chloride in anhydrous tetrahydrofuran to obtain a third solution; adding the first solution into the second solution, reacting for about 5-10 min, adding the third solution, reacting for 1-4 hours, and heating to room temperature to obtain a compound D; and/or the presence of a gas in the gas,
the step of oxidative ring closure treatment comprises: adding anhydrous ferric chloride into dichloromethane serving as a solvent, stirring for 30-120 seconds, adding the compound D, and reacting at room temperature for 1-4 hours to obtain a compound E; and/or the presence of a gas in the gas,
the oximation treatment step comprises the following steps: under the protection of nitrogen, adding the compound E and the hydroxylamine hydrochloride into an absolute ethyl alcohol solvent, and heating and refluxing for about 10-40 hours to obtain a compound F; and/or the presence of a gas in the gas,
the step of reduction treatment comprises: adding the compound F into an absolute ethyl alcohol solvent under protective gas, then adding the palladium-carbon catalyst, heating to 60-80 ℃, adding a hydrazine hydrate solution dissolved in absolute ethyl alcohol, and reacting for 24-72 hours at 80-90 ℃ to obtain a compound G; and/or the presence of a gas in the gas,
the step of closed loop processing comprises: under the protection of nitrogen, dissolving the compound G in dichloromethane, adding thionyl chloride and triethylamine at room temperature, and heating and refluxing for 2-10 hours to obtain a compound H; alternatively, the first and second electrodes may be,
dissolving the compound G in absolute ethyl alcohol, heating and refluxing, adding the selenium dioxide aqueous solution, stirring and refluxing for 3-6 hours to obtain a compound H; and/or the presence of a gas in the gas,
the step of formylation treatment comprises: and dissolving the compound H and the phosphorus oxychloride in N, N-dimethylformamide, and heating to 80-90 ℃ to react for 6-24 hours to obtain the aldehyde compound containing the benzoxydiazole unit.
9. The method of claim 8, wherein the benzoxazole-based acceptor material is selected from the group consisting of,
the mol ratio of the bithiophene pyrrole compound to the N-bromosuccinimide is 1: (1-1.4); and/or the presence of a gas in the gas,
the molar amount of the compound B and the lithium diisopropylamide is 1: (1-1.3); and/or the presence of a gas in the gas,
the molar ratio of the compound C, the n-butyllithium, the copper bromide, the lithium bromide and the oxalyl chloride is 1: (1-1.1): (1-1.1): (0.4-0.5); and/or the presence of a gas in the gas,
the molar ratio of the compound D to the anhydrous ferric chloride is 1: (3-6); and/or the presence of a gas in the gas,
the molar weight ratio of the compound E to the hydroxylamine hydrochloride is 1: (2.4-4); and/or the presence of a gas in the gas,
the mass ratio of the hydrazine hydrate to the compound F to the palladium carbon catalyst is (60-300): (20-30): 1; and/or the presence of a gas in the gas,
the volume ratio of the dichloromethane to the thionyl chloride to the triethylamine is (15-60): 10: (2-1), wherein the mass ratio of the compound G to the dichloromethane is 1: (15-45); alternatively, the first and second electrodes may be,
the molar ratio of the compound G to the selenium dioxide is 1 (1-2); and/or the presence of a gas in the gas,
the molar ratio of the compound H to the phosphorus oxychloride is 1 (10-30).
10. An organic solar cell comprising a light trapping active layer, wherein the light trapping active layer comprises the benzoxadiazole based acceptor material according to any one of claims 1-3 or the benzoxadiazole based acceptor material prepared by the method according to any one of claims 4-9.
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